CN110371964A - A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size - Google Patents
A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size Download PDFInfo
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Abstract
The invention belongs to graphene oxide composite material preparation technical field, the preparation method of the graphene oxide composite material of specifically a kind of nanoscale piece diameter size.Using glass Carbon Materials as anode, immerses in electrolyte, be inserted into cathodic counter electrode；Apply voltage between anode and cathode, carries out electrochemical oxidation lift-off processing；Anode material is removed and is distributed in electrolyte by gradually oxidation in electrochemical reaction process；The graphene oxide powder material of nanoscale piece diameter is arrived after electrolyte containing anode release material is centrifuged, cleans, dialyses and is dried.This method aoxidizes stripping technology using the glass Carbon Materials with special irregular flat crystal structure as electrode, by an one-step electrochemistry, and the control preparation of the stannic oxide/graphene nano piece of different flake diameter distributions may be implemented.The present invention has the characteristics that safe and efficient, pollution-free, product purity is high, product non-metallic ion impurity, can be used for the industrialized production of nanoscale grapheme material.
Description
Technical field
The invention belongs to graphene oxide composite material preparation technical field, the oxidation stone of specifically a kind of nanoscale piece diameter size
The preparation method of black alkene material is prepared using the nanocrystalline carbon material of various grain sizes by the method that electrochemical oxidation is removed
The graphene oxide of different flake diameter distributions may be implemented in 100nm stannic oxide/graphene nano piece below, this method in flake diameter distribution
It is prepared by the control of nanometer sheet.
Background technique
Graphene oxide is a kind of important derivatives of graphene, since the carbon atom on its plane lattice is partially oxidized
The oxygen-containing groups such as hydroxyl, epoxy group, carbonyl, carboxyl in grafting, so that grapheme material is changed by surface inertness and hydrophobicity
Surface-active and hydrophily, while it being able to maintain the high-specific surface area of graphene again.Therefore graphene oxide has excellent dispersion
Property, high chemical activity and the characteristics of be easy to functionalization；And its dispersion performance and chemical activity subtracting with graphene oxide size
It is small and improve.The graphene oxide of nanoscale piece diameter has very excellent dispersibility, the specific surface area of chemical activity and superelevation；
Meanwhile quantum confined effect caused by nano-grade size makes it show unique property in fields such as photoelectricity, biologies, by
It is widely used in photoelectric device, solar battery, bioluminescence imaging, drug delivery, biosensor and non-metal catalyst
Etc. technical fields.
The preparation method of conventional nanoscale piece diameter size graphene oxide is the graphite raw material with little crystallite size at present,
Oxidation is carried out under the action of the concentrated sulfuric acid, compound strong oxidizer and pro-oxidant becomes nano oxidized graphite removing acquisition；Or
Using common graphite raw material, oxidation forms micron-scale under the action of the concentrated sulfuric acid, compound strong oxidizer and pro-oxidant
Then graphene oxide recycles the modes such as high-energy ultrasonic, chemical shearing and high-temperature water hot shearing by the oxidation stone of micron-scale
Black alkene cuts into nano-scale graphene oxide.These methods all rely on chemical oxidation treatment, have synthesis technology complicated, quick-fried
The problems such as fried risk is big, environmental pollution is serious, the reaction time is long and low yield；Meanwhile it is equal also to prepare size distribution
Even nanoscale grapheme material.
Electrochemical method has the characteristics that process is simple, be not related to dangerous toxic chemical spills and environmental pollution is small, at present
Have become one of the main method of graphene and the preparation of graphene oxide mass.Academic journals " advanced material " (Y.Sheng
et al..New-Generation Graphene from Electrochemical Approaches:Production and
Applications. " Advanced Materials ", 2016 the 6213-6221 pages of volume 28), summary 2016 years before
Tens kinds of electrochemistry prepare graphene and graphene oxide method, however these methods there are degree of oxidation low, low yield, number of plies
The problems such as thick.Chinese invention patent application (publication number: CN107215867A) discloses a kind of serialization, and to prepare graphene oxide micro-
The method of piece, this method can rapidly and efficiently prepare the graphene oxide of high oxidation degree, however its obtained graphene oxide
Piece diameter in the micron-scale more than, it is difficult to obtain the graphene oxide of nano-grade size.Therefore a kind of be efficiently prepared on a large scale is needed to receive
The new method of meter level piece diameter size graphene oxide.
Summary of the invention
It is an object of the invention to propose a kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size, utilize
Glass Carbon Materials with special irregular flat crystal structure aoxidize stripping technology as electrode, by an one-step electrochemistry
Prepare the graphene oxide composite material with nanoscale piece diameter size；Pass through the regulation to glass carbon feedstock crystallite dimension
Prepare the nanoscale piece diameter size graphene oxide composite material with different flake diameter distributions.
The technical scheme is that
A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size, the glass for being 1~500nm with crystallite dimension
Glass Carbon Materials immerse in electrolyte as anode, are inserted into cathodic counter electrode；Apply voltage between anode and cathode, carries out electrification
Learn oxidation lift-off processing；Anode material is removed and is distributed in electrolyte by gradually oxidation in electrochemical reaction process；To containing
The oxidation stone of nanoscale piece diameter is arrived after having the electrolyte of anode release material to be centrifuged, cleaned, dialysed and be dried
Black alkene powder body material.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, glass Carbon Materials are polyacrylonitrile tree
The complex of one or more of rouge, phenolic resin, asphaltic resin or viscose is carried out by high temperature carbonization and graphitization
It is prepared；Wherein, carbonization temperature is 300~1500 DEG C, and graphitization temperature is 1500~3800 DEG C；The crystal grain of glass carbon material
Size increases with the raising for the treatment of temperature, and the grain size range of gained glass Carbon Materials is that 1~500nm is adjustable.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, it is preferred that carbonization temperature be 800~
1200 DEG C, graphitization temperature is 2000~3300 DEG C, and the crystallite dimension of glass carbon material is 2~50nm.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, electrolyte be acid, alkali and salt wherein
One or two kinds of above non-reaction system mixing；Wherein, acid includes but is not limited to sulfuric acid, hydrochloric acid, acetic acid, trifluoro second
Acid, trifluoromethanesulfonic acid, perchloric acid, chlorosulfonic acid or evil spirit acid, alkali include but is not limited to potassium hydroxide, sodium hydroxide, barium hydroxide or
Ammonium hydroxide, salt include but is not limited to sodium sulphate, ammonium sulfate, potassium hyperchlorate or potassium sulfate；The mass concentration model of electrolyte in electrolyte
Enclose is 0.01%~90%.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, it is preferred that electrolyte in electrolyte
Mass concentration range be 20%~60%.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, the material of cathodic counter electrode include but
It is not limited to platinum filament, copper wire, nickel wire, spun gold, stainless steel wire or graphite rod, centered on glassy carbon electrode, glass is placed in electrode
It is 1mm~1m to electrode and glassy carbon electrode surface distance range around carbon resistance rod；Applying voltage between cathode, anode is
Continuous DC voltage, pulsed dc voltage or alternating voltage, voltage range are 0.1~20kV.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, it is preferred that electrode and glass-like carbon
Electrode surface distance range is 5mm~50mm, and voltage range is 2~5V.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, nanoscale piece diameter graphene oxide phase
40% is greater than for the yield weight ratio of glass carbon feedstock, graphene oxide alkene single layer rate is greater than 60%, graphene oxide sheet diameter
Range is 1~500nm, and the similitude of the crystal particle scale distribution of graphene oxide product flake diameter distribution and base glass Carbon Materials is big
In 70%.
The preparation method of the graphene oxide composite material of the nanoscale piece diameter size, it is preferred that nanoscale piece diameter oxidation
Graphene relative to glass carbon feedstock yield weight ratio be 50%~160%, graphene oxide alkene single layer rate be 70%~
100%, graphene oxide sheet diameter range is 2~50nm, the crystalline substance of graphene oxide product flake diameter distribution and base glass Carbon Materials
The proportional similarity of grain size distribution is 75%~100%.
Technical principle of the invention is:
As shown in Figure 1, using glass-like carbon electrolytic preparation nano-scale graphene oxide process schematic, the glass-like carbon electricity
Pole (glass charcoal) is that accumulation is mutually wound by microlite ink sheet into (Fig. 2), and chemical property is stablized, anti-oxidant and impermeabilisation ability
By force, even if can not be by negative ions and molecule intercalation applying very high voltage, therefore the glassy carbon electrode had been electrolysed
Electrode structure remains that stabilization is not crushed by negative ions and molecule intercalation in journey.Apply anode electricity on glassy carbon electrode
Position, surface will aoxidize in aqueous electrolyte, with the bubble of surface generation, oxide layer be graphene oxide from
Electrode surface is off into electrolyte, and oxidation stripping reaction is remained to be carried out inward by electrode surface, glassy carbon electrode thickness
As the extension of electrolysis time is thinning, due to there is not scaling-off, quick peeling phenomenon, the reaction process oxidation reaction is filled
Point, the graphene of high oxidation degree can be efficiently prepared, carbon-to-oxygen ratio is up to 1.3.Since glass-like carbon itself is by nanocrystalline
Graphite flake composition, graphite chip size limits final graphene oxide size, therefore can prepare the oxidation of nano-grade size
Graphene, the size that nanoscale graphene can be effectively controlled by regulating and controlling graphite chip size are distributed.
Advantages of the present invention and the utility model has the advantages that
1. not introducing heavy metal ion in process of the present invention, without reference to nitrogen oxides, toxic and harmful gas will not be generated,
Free from environmental pollution, preparation process is simple, is easy to large scale preparation.
2. nanoscale graphene yield prepared by the present invention is greater than 40%, carbon-to-oxygen ratio can achieve 1.3, and single layer rate is super
Cross 60%.
3. nanoscale graphene size adjustable prepared by the present invention, range is 2~50nm.
4. the present invention has the characteristics that safe and efficient, pollution-free, product purity is high, product non-metallic ion impurity, can use
In the industrialized production of nanoscale grapheme material.
Detailed description of the invention
Fig. 1 prepares the process schematic of nano-scale graphene oxide using glass-like carbon.
The typical high resolution transmission electron microscopy pattern photo of Fig. 2 glass Carbon Materials.
Nano graphene oxide high resolution transmission electron microscopy pattern photo in Fig. 3 embodiment 1.
Specific embodiment
In the specific implementation process, the present invention immerses electricity using the glass Carbon Materials with specific die size as anode
It solves in liquid, is inserted into cathodic counter electrode；Apply voltage between anode and cathode, carries out electrochemical oxidation lift-off processing；Anode material
It is removed and is distributed in electrolyte by gradually oxidation in electrochemical reaction process.To the electrolyte containing anode release material into
After the conventional treatments such as row centrifugation, cleaning, dialysis and drying, the graphene oxide powder material of nanoscale piece diameter can be obtained.
Drawings and examples of the present invention are described in further detail to a specific embodiment of the invention, below
Three embodiments but are not intended to limit the scope of the invention for explanation of the invention.
Embodiment 1.
In the present embodiment, using polyacrylonitrile resin as raw material, carbonized by 1000 DEG C, then using 1200 DEG C of graphite
Change, obtain the glassy carbon electrode that crystallite dimension is 1~10nm, using the glassy carbon electrode as electrolysis raw material, electrode is used
Platinum electrode, distance 20mm between glassy carbon electrode and platinum electrode.Electrolyte selects the aqueous sulfuric acid of 50wt%, glass-like carbon
Electrode and between electrode apply 3.5V continuous DC voltage (Fig. 1).After glassy carbon electrode is oxidized completely have been removed, take
It out containing the electrolyte of graphene oxide, is centrifuged by the revolving speed of 15000RPM, supernatant recycles and reuses, and sediment passes through
Washing is centrifuged again, is finally dialysed, and then freeze-drying obtains graphene oxide powder.Obtained graphene oxide powder and consumption glass
Glass charcoal weight ratio is 60%, and obtained graphite oxide single layer rate is 90%, and flake diameter distribution is 1~6nm, and average piece diameter is 4nm.
As shown in figure 3, nano graphene oxide high resolution transmission electron microscopy pattern photo can from embodiment 1
Out, the piece diameter of gained nano graphene oxide is mainly distributed on 1~6nm.
Embodiment 2.
In the present embodiment, using phenolic resin as raw material, is carbonized by 1000 DEG C, be then graphitized, obtain using 1800 DEG C
The glassy carbon electrode for being 5~20nm to crystallite dimension, using the glassy carbon electrode as electrolysis raw material, to electrode using platinum filament electricity
Pole, distance 20mm between glassy carbon electrode and platinum electrode.Electrolyte select 50wt% aqueous sulfuric acid, glassy carbon electrode with
To the pulsed dc voltage (Fig. 1) for applying 3.5V between electrode.After glassy carbon electrode is oxidized completely have been removed, taking-up contains
The electrolyte of graphene oxide is centrifuged by the revolving speed of 10000RPM, and supernatant recycles and reuses, and sediment is by washing again
Centrifugation, finally dialyses, and then freeze-drying obtains graphene oxide powder.Obtained graphene oxide powder and consumption glass-like carbon weight
Amount ratio is 65%, and obtained graphite oxide single layer rate is 80%, and flake diameter distribution is 4~16nm, and average piece diameter is 9nm.
Embodiment 3.
In the present embodiment, using asphaltic resin as raw material, is carbonized by 1000 DEG C, be then graphitized, obtain using 2200 DEG C
The glassy carbon electrode for being 15~40nm to crystallite dimension uses platinum filament to electrode using the glassy carbon electrode as electrolysis raw material
Electrode, distance 20mm (Fig. 1) between glassy carbon electrode and platinum electrode.Electrolyte selects the aqueous sulfuric acid of 50wt%, glass
Carbon resistance rod and between electrode apply 3.5V continuous DC voltage.After glassy carbon electrode is oxidized completely have been removed, take out
Electrolyte containing graphene oxide is centrifuged by the revolving speed of 10000RPM, and supernatant recycles and reuses, and sediment is by washing
It washs and is centrifuged again, finally dialyse, then freeze-drying obtains graphene oxide powder.Obtained graphene oxide powder and consumption glass
Charcoal weight ratio is 70%, and obtained graphite oxide single layer rate is 70%, and flake diameter distribution is 8~25nm, and average piece diameter is 15nm.
Embodiment 4.
In the present embodiment, using polyacrylonitrile resin as raw material, carbonized by 1000 DEG C, then using 2600 DEG C of graphite
Change, obtain the glassy carbon electrode that crystallite dimension is 30~100nm, using the glassy carbon electrode as electrolysis raw material, electrode is adopted
With platinum electrode, distance 20mm (Fig. 1) between glassy carbon electrode and platinum electrode.Electrolyte selects the sulfuric acid of 50wt% water-soluble
Liquid, glassy carbon electrode and the pulsed dc voltage to application 3.5V between electrode.It has been removed when glassy carbon electrode is oxidized completely
Afterwards, the electrolyte containing graphene oxide is taken out, is centrifuged by the revolving speed of 10000RPM, supernatant recycles and reuses, and precipitates
Object is centrifuged again by washing, is finally dialysed, and then freeze-drying obtains graphene oxide powder.Obtained graphene oxide powder with
Consuming glass-like carbon weight ratio is 72%, and obtained graphite oxide single layer rate is 70%, and flake diameter distribution is 12~40nm, average piece diameter
For 25nm.
Embodiment 5.
In the present embodiment, using mass ratio be the polyacrylonitrile resin of 1:1, phenolic resin is raw material, by 900 DEG C of charcoals
Change, be then graphitized using 2800 DEG C, obtain the glassy carbon electrode that crystallite dimension is 30~150nm, utilizes glass-like carbon electricity
Pole uses platinum electrode, distance 10mm (Fig. 1) between glassy carbon electrode and platinum electrode as electrolysis raw material, to electrode.Electrolysis
Liquid selects the sodium hydrate aqueous solution of 10wt%, glassy carbon electrode and the continuous DC voltage to application 2V between electrode.Work as glass
Glass carbon resistance rod is oxidized completely removed after, take out the electrolyte containing graphene oxide, by 12000RPM revolving speed be centrifuged,
Supernatant recycles and reuses, and sediment is centrifuged again by washing, finally dialyses, and then freeze-drying obtains graphene oxide powder
End.Obtained graphene oxide powder and consumption glass-like carbon weight ratio are 55%, and obtained graphite oxide single layer rate is 86%, piece diameter
It is distributed as 20~150nm, average piece diameter is 55nm.
Embodiment 6.
In the present embodiment, using mass ratio be the phenolic resin of 1:1, asphaltic resin is raw material, carbonized by 1200 DEG C, so
Afterwards using 3000 DEG C be graphitized, obtain crystallite dimension be 50~300nm glassy carbon electrode, using the glassy carbon electrode as
It is electrolysed raw material, platinum electrode, distance 30mm (Fig. 1) between glassy carbon electrode and platinum electrode are used to electrode.Electrolyte is selected
The potassium hyperchlorate aqueous solution of 40wt%, glassy carbon electrode and the pulsed dc voltage to application 4V between electrode.When glass-like carbon electricity
It is extremely oxidized completely after having removed, takes out the electrolyte containing graphene oxide, be centrifuged by the revolving speed of 9000RPM, supernatant
It recycles and reuses, sediment is centrifuged again by washing, is finally dialysed, and then freeze-drying obtains graphene oxide powder.Institute
Obtaining graphene oxide powder and consumption glass-like carbon weight ratio is 65%, and obtained graphite oxide single layer rate is 96%, flake diameter distribution
For 40~150nm, average piece diameter is 80nm.
The above results show that graphene oxide preparation process of the invention is simple, easily-controllable, can real high yield production system
It is standby, and graphene oxide sized nanostructures grade is adjustable, has great application value.The four above embodiments are to of the invention
It further illustrates, each electrolysis link therein can do several transformation and improvement, in the change for the principle for not departing from the technology of the present invention
It changes and improves, also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size, which is characterized in that with crystallite dimension be 1~
The glass Carbon Materials of 500nm immerse in electrolyte as anode, are inserted into cathodic counter electrode；Apply voltage between anode and cathode,
Carry out electrochemical oxidation lift-off processing；Anode material is removed by gradually oxidation in electrochemical reaction process and is distributed to electrolyte
In；After electrolyte containing anode release material is centrifuged, is cleaned, is dialysed and is dried to get arrive nanoscale piece diameter
Graphene oxide powder material.
2. the preparation method of the graphene oxide composite material of nanoscale piece diameter size described in accordance with the claim 1, which is characterized in that
Glass Carbon Materials are the complex of one or more of polyacrylonitrile resin, phenolic resin, asphaltic resin or viscose, warp
It crosses high temperature carbonization and graphitization is prepared；Wherein, carbonization temperature be 300~1500 DEG C, graphitization temperature be 1500~
3800℃；The crystallite dimension of glass carbon material increases, the crystallite dimension model of gained glass Carbon Materials with the raising for the treatment of temperature
Enclose for 1~500nm it is adjustable.
3. the preparation method of the graphene oxide composite material of nanoscale piece diameter size according to claim 2, which is characterized in that
Preferably, carbonization temperature is 800~1200 DEG C, and graphitization temperature is 2000~3300 DEG C, and the crystallite dimension of glass carbon material is 2
~50nm.
4. the preparation method of the graphene oxide composite material of nanoscale piece diameter size described in accordance with the claim 1, which is characterized in that
Electrolyte is acid, alkali and salt is one such or the mixing of two or more non-reaction systems；Wherein, acid includes but is not limited to sulphur
Acid, hydrochloric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, perchloric acid, chlorosulfonic acid or evil spirit acid, alkali include but is not limited to potassium hydroxide,
Sodium hydroxide, barium hydroxide or ammonium hydroxide, salt include but is not limited to sodium sulphate, ammonium sulfate, potassium hyperchlorate or potassium sulfate；In electrolyte
The mass concentration range of electrolyte is 0.01%~90%.
5. the preparation method of the graphene oxide composite material of nanoscale piece diameter size according to claim 4, which is characterized in that
Preferably, the mass concentration range of electrolyte is 20%~60% in electrolyte.
6. the preparation method of the graphene oxide composite material of nanoscale piece diameter size described in accordance with the claim 1, which is characterized in that
The material of cathodic counter electrode includes but is not limited to platinum filament, copper wire, nickel wire, spun gold, stainless steel wire or graphite rod, with glassy carbon electrode
Centered on, electrode is placed in around glassy carbon electrode, is 1mm~1m to electrode and glassy carbon electrode surface distance range；Yin
Applying voltage between pole, anode is continuous DC voltage, pulsed dc voltage or alternating voltage, voltage range is 0.1~
20kV。
7. the preparation method of the graphene oxide composite material of nanoscale piece diameter size according to claim 6, which is characterized in that
It preferably, is 5mm~50mm to electrode and glassy carbon electrode surface distance range, voltage range is 2~5V.
8. the preparation method of the graphene oxide composite material of nanoscale piece diameter size described in accordance with the claim 1, which is characterized in that
Nanoscale piece diameter graphene oxide is greater than 40% relative to the yield weight ratio of glass carbon feedstock, and graphene oxide alkene single layer rate is big
In 60%, graphene oxide sheet diameter range is 1~500nm, graphene oxide product flake diameter distribution and base glass Carbon Materials
The similitude of crystal particle scale distribution is greater than 70%.
9. the preparation method of the graphene oxide composite material of nanoscale piece diameter size described in accordance with the claim 1, which is characterized in that
Preferably, nanoscale piece diameter graphene oxide is 50%~160% relative to the yield weight ratio of glass carbon feedstock, graphite oxide
Alkene alkene single layer rate be 70%~100%, graphene oxide sheet diameter range be 2~50nm, graphene oxide product flake diameter distribution with
The proportional similarity of the crystal particle scale distribution of base glass Carbon Materials is 75%~100%.
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| CN115536018A (en) * | 2022-09-30 | 2022-12-30 | 深圳市贝特瑞新能源技术研究院有限公司 | Graphene oxide slurry, heat-conducting film and preparation method |
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| CN113830760A (en) * | 2021-10-26 | 2021-12-24 | 深圳烯材科技有限公司 | Method for preparing graphene oxide through stable electrolysis |
| CN113830760B (en) * | 2021-10-26 | 2023-09-22 | 深圳烯材科技有限公司 | Method for preparing graphene oxide by stable electrolysis |
| CN115536018A (en) * | 2022-09-30 | 2022-12-30 | 深圳市贝特瑞新能源技术研究院有限公司 | Graphene oxide slurry, heat-conducting film and preparation method |
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